Mixtures of reactive dyes and their use

ABSTRACT

Dye mixtures comprising at least one dye of formula together with at least one dye of formula wherein the radicals indicated in the formulae are defined in accordance with the claims, are suitable for dyeing or printing cellulosic fibre materials with good build-up behaviour and yield dyeings of a deep shade having good fastness properties.

The present invention relates to mixtures of reactive dyes that aresuitable for dyeing or printing nitrogen-containing or hydroxy-groupcontaining fibre materials and yield dyeings or prints having goodall-round fastness properties.

The practice of dyeing has recently led to higher demands being made onthe quality of the dyeings and the profitability of the dyeing process.As a result, there continues to be a need for novel, readily availabledyeing compositions having good properties, especially in respect oftheir application. Dyeing nowadays requires reactive dyes that have, forexample, sufficient substantivity and at the same time good ease ofwashings of unfixed dye. They should also exhibit a good tinctorialyield and high reactivity, the objective being especially to obtaindyeings having high degrees of fixing. In many cases, the build-upbehaviour of reactive dyes is insufficient to meet the demands beingmade, especially when dyeing very deep shades.

The problem underlying the present invention is therefore to provide newmixtures of reactive dyes that are particularly suitable for dyeing andprinting fibre materials and that exhibit the qualities described aboveto a high degree. The dyes should also yield dyeings having goodall-round fastness properties, for example fastness to light and towetting.

The present invention accordingly relates to dye mixtures comprising atleast one dye of formula

together with at least one dye of formula

whereinR₁ and R₂ are each independently of the other hydrogen or unsubstitutedor substituted C₁-C₈alkyl,(R₃)₀₋₃ and (R₄)₀₋₃ each independently of the other denote from 0 to 3identical or different substituents from the group halogen, C₁-C₄alkyl,C₁-C₄alkoxy, carboxy and sulfo,D₁ and D₂ are each independently of the other the radical of a diazocomponent of the benzene or naphthalene series,r and s are each independently of the other the number 0 or 1, and thesum of r+s is the number 1 or 2,Y₁ and Y₂ are each independently of the other a fibre-reactive radicalof formula—SOr₂-Z (3a),—NH—CO—(CH₂)_(m)—SO₂-Z  (3b),—CONH—(CH₂), —SO₂-Z  (3c),—NH—CO—CH(Hal)CH₂-Hal  (3d),—NH—CO—C(Hal)═CH₂  (3e) or

whereinX is halogen, T has independently the same definitions as X, or is anon-fibre-reactive substituent or a fibre-reactive radical of formula—NH—(CH₂)₂₋₃—SO₂-Z  (4a)—NH—(CH₂)₂₋₃—O—(CH₂)₂₋₃—SO₂-Z  (4b),

(R₅)₀₋₂ denotes from 0 to 2 identical or different substituents from thegroup halogen, C₁-C₄alkyl, C₁-C₄alkoxy and sulfo,Z is vinyl or a radical —CH₂—CH₂—U and U is a group removable underalkaline conditions,Q is a group —CH(Hal)-CH₂-Hal or —C(Hal)═CH₂,m and n are each independently of the other the number 2, 3 or 4, andHal is halogen,with at least one of the radicals Y₁ and Y₂ being a radical of formula(3f), and the dye of formula (2) not being a dye of formula

whereinX* is fluorine and the β-sulfatoethylsulfonyl group is bonded in the4-position, orX* is chlorine and the β-sulfatoethylsulfonyl group is bonded in the3-position.

In the radical of formula (4c), Me is a methyl radical and Et is anethyl radical. The mentioned radicals come into consideration, inaddition to hydrogen, as substituents on the nitrogen atom.

As C₁-C₈alkyl there come into consideration for R₁ and R₂, eachindependently of the other, for example, methyl, ethyl, propyl,isopropyl, butyl, sec-butyl, tertbutyl, isobutyl, n-pentyl, n-hexyl,n-heptyl or n-octyl. Of interest is a C₁-C₄alkyl radical. The mentionedalkyl radicals may be unsubstituted or substituted, for example, byhydroxy, sulfo, sulfato, cyano, carboxy, C₁-C₄alkoxy or by phenyl,preferably by hydroxy, sulfate, C₁-C₄alkoxy or by phenyl. Preference isgiven to the corresponding unsubstituted radicals.

As C₁-C₄alkyl there come into consideration for R₃, R₄ and R₅, eachindependently of the others, for example, methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, tertbutyl or isobutyl, preferably methylor ethyl and especially methyl.

As C₁-C₄alkoxy there come into consideration for R₃, R₄ and R₅, eachindependently of the others, for example, methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy or isobutoxy, preferably methoxy or ethoxy andespecially methoxy.

As halogen there come into consideration for R₃, R₄ and R₅, eachindependently of the others, for example, fluorine, chlorine or bromine,preferably chlorine or bromine and especially chlorine.

Preferably one of the radicals R₁ and R₂ is hydrogen and the other isone of the above-mentioned unsubstituted or substituted C₁-C₈alkylradicals.

R₁ and R₂ are especially hydrogen.

(R₃)₀₋₃ and (R₄)₀₋₃ each independently of the other preferably denotefrom 0 to 3 identical or different substituents from the groupC₁-C₄alkyl, C₁-C₄alkoxy and sulfo. In an interesting embodiment, each ofR₃ and R₄ is a sulfo group.

(R₅)₀₋₂ preferably denotes from 0 to 2 identical or differentsubstituents from the group C₁-C₄alkyl, C₁-C₄alkoxy and sulfo,especially methyl, methoxy and sulfo.

R₅ is especially hydrogen.

The radicals D₁ and D₂ In the dye mixtures according to the inventionmay comprise substituents customary for azo dyes.

Examples from the range of substituents that may be mentioned include:alkyl groups having from 1 to 12 carbon atoms, especially from 1 to 4carbon atoms, such as methyl, ethyl, n- or iso-propyl, or n-, iso, sec-or tert-butyl, alkoxy groups having from 1 to 8 carbon atoms, especiallyfrom 1 to 4 carbon atoms, such as methoxy, ethoxy, n- or isopropoxy, orn-, iso-, sec- or tert-butoxy, C₁-C₄alkoxy substituted in the alkylmoiety, for example by hydroxy, C₁-C₄alkoxy or by sulfato, e.g.2-hydroxyethoxy, 3-hydroxypropoxy, 2-sulfatoethoxy, 2-methoxyethoxy or2-ethoxyethoxy, alkanoylamino groups having from 2 to 8 carbon atoms,especially C₂-C₄alkanoylamino groups such as acetylamino orpropionylamino, benzoylamino or C₂-C₄alkoxycarbonylamino groups such asmethoxycarbonylamino or ethoxycarbonyl-amino, amino, N-mono- orN,N-di-C₁-C₄alkylamino each unsubstituted or substituted in the alkylmoiety, for example, by hydroxy, sulfo, sulfato or by C₁-C₄alkoxy, e.g.methylamino, ethylamino, N,N-dimethyl- or N,N-diethylamino,sulfomethylamino, β-hydroxyethylamino, N,N-di(β-hydroxyethylamino),N-β-sulfatoethylamino, phenylamino unsubstituted or substituted in thephenyl moiety by methyl, methoxy, halogen or by sulfo,N—C₁-C₄alkyl-N-phenylamino unsubstituted or substituted in the alkylmoiety by hydroxy, sulfo or by sulfato or substituted in the phenylmoiety by methyl, methoxy, halogen or by sulfo, e.g.N-methyl-N-phenylamino, N-ethyl-N-phenylamino,N-β-hydroxyethyl-N-phenylamino or N-β-sulfoethyl-N-phenylamino,unsubstituted or sulfo-substituted naphthylamino, alkanoyl groups havingfrom 2 to 8 carbon atoms, especially from 2 to 4 carbon atoms, e.g.acetyl or propionyl, benzoyl, alkoxycarbonyl having from 1 to 4 carbonatoms in the alkoxy radical, such as methoxycarbonyl or ethoxycarbonyl,alkylsulfonyl having from 1 to 4 carbon atoms, such as methylsulfonyl orethylsulfonyl, phenyl- or naphthyl-sulfonyl, trifluoromethyl, nitro,cyano, hydroxy, halogen, such as fluorine, chlorine or bromine,carbamoyl, N-C₁-C₄alkylcarbamoyl, such as N-methylcarbamoyl orN-methylcarbamoyl, sulfamoyl, N—C₁-C₄alkylsulfamoyl such asN-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl,N-isopropylsulfamoyl or N-butyl-sulfamoyl, N—(β-hydroxyethyl)sulfamoyl,N,N-di(β-hydroxyethyl)sulfamoyl, N-phenylsulfamoyl, ureido, carboxy,sulfomethyl, sulfo or sulfato and also fibre-reactive radicals. Thealkyl radicals may additionally be interrupted by oxygen (—O—) or anamino group (—NH—, —N(C₁-C₄-alkyl)-).

In an interesting embodiment of the present invention, at least one ofthe radicals D₁ and D₂ carries at least one fibre-reactive group.

In a further interesting embodiment of the present invention, each ofthe radicals D₁ and D₂ carries at least one fibre-reactive group.

Fibre-reactive radicals are to be understood as being those which arecapable of reacting with the hydroxy groups of cellulose, with theamino, carboxy, hydroxy and thiol groups in wool and silk or with theamino and possibly carboxy groups of synthetic polyamides to formcovalent chemical bonds. The fibre-reactive radicals are generallybonded to the dye radical directly or via a bridging member. Suitablefibre-reactive radicals are, for example, those having at least oneremovable substituent on an aliphatic, aromatic or heterocyclic radicalor those wherein the mentioned radicals contain a radical suitable forreaction with the fibre material, for example a vinyl radical.

Such fibre-reactive radicals are known per se and a large number of themare described, e.g. in Venkataraman “The Chemistry of Synthetic Dyes”volume 6, pages 1-209, Academic Press, New York, London 1972 or in U.S.Pat. No. 5,684,138.

D₁ and D₂ are preferably each independently of the other a radical offormula

wherein(R₆)₀₋₃ denotes from 0 to 3 identical or different substituents from thegroup halogen, C₁-C₄-alkyl, C₁-C₄alkoxy, carboxy, nitro and sulfo,especially halogen, C₁-C₄alkyl, C₁-C₄alkoxy and sulfo, andY₃ is a radical of the above-mentioned formula (3a), (3b), (3c), (3d),(3e) or (3f).X in the fibre-reactive radical of formula (3f) is, for example,fluorine, chlorine or bromine, preferably fluorine or chlorine andespecially chlorine.T is preferably a non-fibre-reactive substituent or a fibre reactiveradical of formula (4a), (4b), (4c), (4d) or (4e) and is especially afibre-reactive radical of formula (4a), (4b), (4c), (4d) or (4e).When T is a non-fibre-reactive substituent, that substituent may be, forexample hydroxy; C₁-C₄alkoxy, C₁-C₄alkylthio unsubstituted orsubstituted, for example, by hydroxy, carboxy or by sulfo; amino; aminothat is mono- or di-substituted by C₁-C₈alkyl, it being possible for thealkyl to be unsubstituted or further substituted, for example by sulfo,sulfato, hydroxy, carboxy or by phenyl, especially by sulfo or hydroxy,and interrupted one or more times by the radical —O—; cyclohexylamino;morpholino; N—C₁-₄alkyl-N-phenylamino or phenylamino or naphthylamino,the phenyl or naphthyl being unsubstituted or substituted, for example,by C₁-C₄alkyl, C₁-C₄alkoxy, carboxy, sulfo or by halogen.

Examples of suitable non-fibre-reactive substituents T are amino,methylamino, ethylamino, β-hydroxyethylamino,N-methyl-N-β-hydroxyethylamino, N-ethyl-N-β-hydroxyethylamino,N,N-di-β-hydroxyethylamino, β-sulfoethylamino, cyclohexylamino,morpholino, 2-, 3- or 4-chlorophenylamino, 2-, 3- or4-methylphenylamino, 2-, 3- or 4-methoxyphenylamino, 2-, 3- or4-sulfophenylamino, disulfophenylamino, 2-, 3- or 4-carboxyphenylamino,1- or 2-naphthyl-amino, 1-sulfo-2-naphthylamino,4,8-disulfo-2-naphthylamino, N-ethyl-N-phenylamino,N-methyl-N-phenylamino, methoxy, ethoxy, n- or iso-propoxy and hydroxy.

As a non-fibre-reactive substituent, T is preferably C₁-C₄alkoxy,C₁-C₄alkylthio unsubstituted or substituted by hydroxy, carboxy or bysulfo, hydroxy, amino, N-mono- or N,N-di-C₁-C₄-alkylamino eachunsubstituted or substituted in the alkyl moiety by hydroxy, sulfato orby sulfo, morpholino, phenylamino unsubstituted or substituted in thephenyl ring by sulfo, carboxy, acetylamino, chlorine, methyl or bymethoxy, or N—C₁-C₄alkyl-N-phenylamino unsubstituted or substituted inthe same manner, the alkyl being unsubstituted or substituted byhydroxy, sulfo or by sulfato, or naphthylamino unsubstituted orsubstituted by from 1 to 3 sulfo groups.

Especially preferred non-fibre-reactive substituents T are amino,N-methylamino, N-ethylamino, N-β-hydroxyethylamino,N-methyl-N-β-hydroxyethylamino, N-ethyl-N-β-hydroxyethylamino,N,N-di-β-hydroxyethylamino, β-sulfoethylamino, morpholino, 2-, 3- or4-carboxyphenylamino, 2-, 3 or 4-sulfophenylamino andN—C₁-C₄alkyl-N-phenylamino.

In the case of the fibre-reactive radicals T of formulae (4a) and (4b),Z is preferably β-chloroethyl. In the case of the fibre-active radicalsT of formulae (4c) and (4d), Z is preferably vinyl or β-sulfatoethyl.

When T is a fibre-reactive radical, T is preferably a radical of formula(4c) or (4d), especially of formula (4c).

Hal in the fibre-reactive radicals of formulae (3d), (3e) and (4e) ispreferably chlorine or bromine, especially bromine.

As leaving group U there come into consideration, for example, —Cl, —Br,—F, —OSO₃H, —SSO₃H, —OCO—CH₃, —OPO₃H₂, —OCO—C₆H₅, OSO₂-C₁-C₄alkyl or—OSO₂—N(C₁-C₄alkyl)₂. U is preferably a group of formula —Cl, —OSO₃H,—SSO₃H, —OCO—CH₃, —OCO—C₆H₅ or —OPO₃H₂, especially —Cl or —OSO₃H andpreferably —OSO₃H.

Examples of suitable radicals Z are accordingly vinyl, β-bromo- orβ-chloro-ethyl, β-acetoxyethyl, β-benzoyloxyethyl, β-phosphatoethyl,β-sulfatoethyl and β-thiosulfatoethyl. Z is preferably vinyl,β-chloroethyl or β-sulfatoethyl.

D₁ and D₂ are each independently of the other preferably a radical offormula

especially of formula (5a), (5b) or (5e), wherein(R_(6a))_(0.2) denotes from 0 to 2 identical or different substituentsfrom the group halogen,C₁-C₄alkyl, C₁-C₄alkoxy and sulfo, especially methyl, methoxy and sulfo,Y_(3a) is α, β-dibromopropionylamino or α-bromoacryloylamino,m is the number 2 or 3, especially 3,n is the number 2 or 3, especially 2, andZ₁, Z₂, Z₃ and Z₄ are each independently of the others vinyl,β-chloroethyl or β-sulfatoethyl.

Z₁ and Z₂ are preferably each independently of the other vinyl orβ-sulfatoethyl.

Z₃ is preferably β-chloroethyl or β-sulfatoethyl, especiallyβ-chloroethyl.

Z₄ is preferably β-chloroethyl or β-sulfatoethyl, especiallyβ-sulfatoethyl.

Each of r and s is preferably the number 1 and the sum of r+s is thenumber 2.

Preference is given to the dyes of formula (1) wherein

R₁ and R₂ are hydrogen, and

D₁ and D₂ are each independently of the other a radical of formula (5a),(5b), (5c), (5d) or (5e), preferably of formula (5a), (5b) or (5e) andespecially of formula (5a).

The radicals D₁ and D₂ In the dyes of formula (1) are identical ornon-identical, preferably non-identical.

Special preference is given to the dyes of formula (1) wherein

R₁ and R₂ are hydrogen,

D₁ is a radical of formula

D₂ is a radical of formula

whereinR_(6a) and R_(6b) are each independently of the other methyl or methoxy,R_(6a) is especially methyl and R_(6b) is especially methoxy, andZ_(1a) and Z_(1b) are each independently of the other vinyl,β-chloroethyl or β-sulfatoethyl.

The dye of formula (1) may also be a dye mixture comprising at least onecompound of formulae (1a) and (1b)

together with at least one compound of formulae (1c) and (1d)

whereinD₁ and D₂ are non-identical, andR₁, R₂, D₁ and D₂ have the definitions and preferred meanings givenabove.

Preference is given to the dyes of formula (2) wherein

(R₃)_(0.3) and (R₄)₀₋₃ have the definitions and preferred meanings givenabove, each of r and s is the number 1 and the sum of r+s is the number2, and one of the fibre-reactive radicals Y₁ and Y₂ is a radical offormula (3a), (3b), (3c), (3d) or (3e),

and the other of the fibre-reactive radicals Y₁ and Y₂ is a radical offormula (3f), Y₁ is

especially a radical of formula (3f) and Y₂ is especially a radical offormula (3a), (3b), (3c), (3d) or (30), more especially (3a), whereinthe definitions and preferred meanings given above apply for thefibre-reactive radicals of formulae (3a), (3b), (3c), (3d), (3a) and(3f). In an interesting embodiment, each of R₃ and R₄ is a sulfo group.

An especially preferred dye of formula (2) is a dye of formula

wherein(R₃)₀₋₂ and (R₄)₀₋₂ each independently of the other denote from 0 to 2identical or different substituents selected from the group C₁-C₄alkyl,C₁-C₄alkoxy and sulfo, especially methyl, methoxy and sulfo, andone of the fibre-reactive radicals Y₁ and Y₂ is a radical of formula(3a), (3b), (3c), (3d) or (3e), and the other of the fibre-reactiveradicals Y₁ and Y₂ is a radical of formula (3f), Y₁ is especially aradical of formula (3f) and Y₂ is especially a radical of formula (3a),(3b), (3c), (3d) or (3e), more especially (3a), the definitions andpreferred meanings given above applying for the fibre-reactive radicalsof formulae (3a), (3b), (3c), (3d), (3e) and (3f).

A more especially preferred dye of formula (2) is a dye of formula

whereinX is halogen, especially chlorine, andZ₅ and Z₈ each independently of the other have the definitions andpreferred meanings given above for Z and are especially vinyl orβ-sulfatoethyl.

The dye mixtures according to the invention can be prepared, forexample, by mixing the individual dyes. That mixing process is carriedout, for example, in suitable mills, e.g. ball mills or pin mills, andalso in kneaders or mixers.

Some of the dyes of formulae (1) and (2) are known or can be preparedaccording to processes known per se. Dyes of formula (1) and mixtures ofdyes of formulae (1a), (1b), (1c) and (1d) are disclosed, for example,in WO-A-00/06652. Dyes of formula (2) are described, for example, inU.S. Pat. No. 4,622,390.

The present invention relates also to the novel dye of theabove-mentioned formula (2aa),

wherein

the respective definitions and preferred meanings given above apply forX, Z₅ and Z₆.

The dye of formula (2aa) according to the invention is prepared, forexample, by reacting with one another in suitable order approximately 1molar equivalent each of a compound of formula

wherein X, Z₅ and Z₆ have the respective definitions and preferredmeanings given above.

Suitable as a cyanuric halide of formula (9) is cyanuric chloride orcyanuric fluoride, especially cyanuric chloride.

Since the above-mentioned process steps can be carried out in differentorders, if desired simultaneously, different process variants arepossible. Generally the reaction is carried out stepwise, the order inwhich the simple reactions between the individual reaction componentsare carried out advantageously being selected according to the specificconditions. In a preferred embodiment

(i) approximately one molar equivalent of a compound of formula (6) isdiazotised and coupled with approximately one molar equivalent of acompound of formula (7);

(ii) approximately one molar equivalent of a compound of formula (8) iscondensed with approximately one molar equivalent of a compound offormula (9);

(iii) approximately one molar equivalent of a compound of formula (10)is reacted with approximately one molar equivalent of the compoundobtained according to (ii) to form a secondary condensation product; and

(iv) approximately one molar equivalent of the secondary condensationproduct obtained according to (iii) is diazotised and coupled with thecompound obtained according to (i).

The diazotisation and coupling are carried out in customary manner, forexample by diazotising the compound of formula (6) and the secondarycondensation product obtained according to (iii) in a mineral acidsolution, for example in a hydrochloric acid solution, with a nitrite,e.g. sodium nitrite, at low temperature, e.g. at from 0 to 5° C., andthen coupling with the appropriate coupling component in a neutral toslightly acidic medium, e.g. at a pH of from 3 to 7, preferably from 3to 4 or from 5.5. to 6.5, and at low temperatures, e.g. from 0 to 30° C.

The condensation reactions are generally carried out analogously toknown processes, generally in an aqueous solution at temperatures of,for example, from 0 to 50° C. and at a pH value of, for example, from 3to 10.

The compounds of formulae (6), (7), (8), (9) and (10) are known or canbe prepared analogously to known compounds.

The reactive dyes of formulae (1) and (2) in the dye mixtures accordingto the invention contain sulfo groups which are each present either infree sulfonic acid form or, preferably, in salt form, e.g. in the formof a sodium, lithium, potassium or ammonium salt or a salt of an organicamine, e.g. in triethanolammonium salt form.

The reactive dyes of formulae (1) and (2) and accordingly also the dyemixtures may comprise further additives, e.g. sodium chloride ordextrin.

The dyes of formulae (1) and (2) are present in the dye mixtureaccording to the invention in a ratio by weight of, for example, from1:99 to 99:1, preferably from 5:95 to 95:5 and especially from 10:90 to90:10.

Where appropriate the dye mixtures according to the invention and thereactive dyes of formula (2aa) according to the invention may comprisefurther adjuvants that, for example, improve handling or increase thestorage stability, for example buffers, dispersants or dust-removingagents. Such adjuvants are known to the person skilled in the art.

The dye mixtures according to the invention and the dyes of formula(2aa) according to the invention are suitable for dyeing and printing anextremely wide variety of materials, such as hydroxyl-group-containingor nitrogen-containing fibre materials. Examples are silk, leather,wool, polyamide fibres and polyurethanes and especially cellulosic fibrematerials of all kinds. Such cellulosic fibre materials are, forexample, the natural cellulosic fibres, such as cotton, linen and hemp,and also cellulose and regenerated cellulose. The dye mixtures accordingto the invention and the dyes according to the invention are alsosuitable for dyeing or printing hydroxyl-group-containing fibres presentin blend fabrics, e.g. mixtures of cotton with polyester fibres orpolyamide fibres. The dye mixtures according to the invention and thedyes according to the invention are especially suitable for dyeing orprinting cellulosic fibre materials, especially those containing cotton.They can also be used to dye or print natural or synthetic polyamidefibre materials.

The present invention accordingly relates also to the use of the dyemixtures according to the invention and the dyes of formula (2aa)according to the invention in the dyeing or printing ofhydroxyl-group-containing or nitrogen-containing, especially cellulosic,fibre materials.

The dye mixtures according to the invention and the dyes of formula(2aa) according to the invention can be applied to the fibre materialand fixed to the fibre in a variety of ways, especially in the form ofaqueous dye solutions and print pastes. They are suitable both for theexhaust process and for dyeing in accordance with the pad-dyeingprocess, according to which the goods are impregnated with aqueous,where appropriate salt-containing, dye solutions, and the dyes are fixedafter alkali treatment or in the presence of an alkali, whereappropriate with the action of heat or by storing at room temperaturefor several hours. After fixing, the dyeings or prints are rinsedthoroughly with cold and hot water, if desired with the addition of anagent that acts as a dispersant and promotes the diffusion of unfixeddye.

The dye mixtures according to the invention and the dyes according tothe invention are distinguished by high reactivity, good fixing capacityand very good build-up capacity. Accordingly they can be used in theexhaust dyeing process at low dyeing temperatures and require only shortsteaming times in the pad-steam process. The degress of fixing are highand unfixed dye can be washed off readily, the difference between thedegree of exhaust and the degree of fixing being remarkably small, thatis to say the soaping loss is very small. The dye mixtures according tothe invention and the dyes according to the invention are alsoespecially suitable for printing, especially on cotton, and also forprinting nitrogen-containing fibres, for example wool or silk or blendfabrics that contain wool or silk.

The dyeings and prints produced using the dye mixtures according to theinvention and the dyes according to the invention have a high tinctorialstrength and a high fibre-dye binding stability in both the acidic andthe alkaline range, as well as good fastness to light and very goodwet-fastness properties, such as fastness to washing, to water, toseawater, to cross-dyeing and to perspiration, and good fastness topleating, to hot pressing and to rubbing. The dyeings obtained exhibitfibre-levelness and surface-levelness.

The dye mixtures according to the invention and the dyes of formula(2aa) according to the invention are also suitable as colorants for usein recording systems. Such recording systems are, for example,commercially available inkjet printers for paper or textile printing, orwriting instruments, such as fountain pens and ballpoint pens andespecially inkjet printers. For that purpose the dye mixture accordingto the invention or the dyes according to the invention is/are firstbrought into a form suitable for use in recording systems. A suitableform is, for example, an aqueous ink that comprises the dye mixtureaccording to the invention or the dyes according to the invention ascolorant. The inks can be prepared in customary manner by mixingtogether the individual constituents in the desired amount of water.

Substrates that come into consideration include the above-mentionedhydroxyl-group-containing or nitrogen-containing fibre materials,especially cellulosic fibre materials. The substrate is preferably atextile fibre material.

Also suitable as substrates are paper or plastics films.

Examples of paper that may be mentioned include commercially availableinkjet paper, photo paper, glossy paper, plastics-coated paper, forexample Epson inkjet paper, Epson photo paper, Epson glossy paper, Epsonglossy film, HP special inkjet paper, Epson photo gloss paper, Ilfordphoto paper. Plastics films are, for example, transparent orcloudy/opaque. Suitable plastics films are, for example, 3M transparencyfilm.

Depending on the type of use, for example textile printing or paperprinting, it may be necessary, for example, to adapt the viscosity orother physical properties of the ink accordingly, especially thoseproperties having an effect on the affinity for the substrate inquestion.

The dyes used in the aqueous inks should preferably have a low saltcontent, that is to say they should have a total content of salts ofless than 0.5% by weight, based on the weight of the dyes. Dyes thathave relatively high salt contents as a result of their preparationand/or as a result of the subsequent addition of diluents can bedesalted, for example, by membrane separation procedures, such asultrafiltration, reverse osmosis or dialysis.

The inks preferably have a total content of dyes of from 1 to 35% byweight, especially from 1 to 30% by weight and preferably from 1 to 20%by weight, based on the total weight of the ink. As a lower limit, alimit of 1.5% by weight, preferably 2% by weight and especially 3% byweight, is preferred.

The inks may comprise water-miscible organic solvents, for exampleC₁-C₄alcohols, such as methanol, ethanol, n-propanol, isopropanol,n-butanol, sec-butanol, tert-butanol and iso-butanol; amides, e.g.dimethylformamide and dimethylacetamide; ketones or ketone alcohols,e.g. acetone and diacetone alcohol; ethers, e.g. tetrahydrofuran anddioxane; nitrogen-containing heterocyclic compounds, e.g.N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidone; polyalkyleneglycols, e.g. polyethylene glycol and polypropylene glycol;C₂-C₆-alkylene glycols and thioglycols, e.g. ethylene glycol, propyleneglycol, butylene glycol, triethylene glycol, thiodiglycol, hexyleneglycol and diethylene glycol; further polyols, e.g. glycerol and1,2,6-hexanetriol; and C₁-C₄alkyl ethers of polyhydric alcohols, e.g.2-methoxy-ethanol, 2-(2-methoxyethoxy)ethanol,2-(2-ethoxyethoxy)ethanol, 2-[2-(2-methoxyethoxy)-ethoxy]ethanol and2-[2-(2-ethoxyethoxy)ethoxy]ethanol; preferably N-methyl-2-pyrrolidone,diethylene glycol, glycerol or especially 1,2-propylene glycol, usuallyin an amount of from 2 to 30% by weight, especially from 5 to 30% byweight and preferably from 10 to 25% by weight, based on the totalweight of the ink.

The inks may also comprise solubilisers, e.g. ε-caprolactam.

The inks may comprise thickeners of natural or synthetic origin interalia for the purpose of adjusting the viscosity.

Examples of thickeners that may be mentioned include commerciallyavailable alginate thickeners, starch ethers or locust bean flourethers, especially sodium alginate on its own or in admixture withmodified cellulose, e.g. methylcellulose, ethylcellulose,carboxymethyl-cellulose, hydroxyethylcellulose,methylhydroxyethylcellulose, hydroxypropyl cellulose or hydroxypropylmethylcellulose, especially with preferably from 20 to 25% by weightcarboxy-methylcellulose. Synthetic thickeners that may be mentioned are,for example, those based on poly(meth)acrylic acids orpoly(meth)acrylamides and also polyalkylene glycols having a molecularweight of e.g. from 2000 to 20 000, for example polyethylene glycol orpoly-propylene glycol or the mixed polyalkylene glycols of ethyleneoxide and propylene oxide.

The inks comprise such thickeners, for example, in an amount of from0.01 to 2% by weight, especially from 0.01 to 1% by weight andpreferably from 0.01 to 0.5% by weight, based on the total weight of theink.

The inks may also comprise buffer substances, e.g. borax, borates,phosphates, poly-phosphates or citrates. Examples that may be mentionedinclude borax, sodium borate, sodium tetraborate, sodium dihydrogenphosphate, disodium hydrogen phosphate, sodium tripolyphosphate, sodiumpentapolyphosphate and sodium citrate. They are used especially inamounts of from 0.1 to 3% by weight, preferably from 0.1 to 1% byweight, based on the total weight of the ink, in order to establish a pHvalue of, for example, from 4 to 9, especially from 5 to 8.5.

As further additives, the inks may comprise surfactants or humectants.

Suitable surfactants include commercially available anionic or non-ionicsurfactants. As humectants in the inks according to the invention therecome into consideration, for example, urea or a mixture of sodiumlactate (advantageously in the form of a 50% to 60% aqueous solution)and glycerol and/or propylene glycol in amounts of preferably from 0.1to 30% by weight, especially from 2 to 30% by weight.

Preference is given to inks having a viscosity of from 1 to 40 mPa·s,especially from 1 to 20 mPa·s and preferably from 1 to 10 mPa·s.

The inks may also comprise customary additives, such as antifoam agentsor especially preservatives that inhibit the growth of fungi and/orbacteria. Such additives are usually used in amounts of from 0.01 to 1%by weight, based on the total weight of the ink.

Preservatives that come into consideration include formaldehyde-yieldingagents, e.g. paraformaldehyde and trioxane, especially aqueous,approximately 30 to 40% by weight formaldehyde solutions, imidazolecompounds, e.g. 2-(4-thiazolyl)benzimidazole, thiazole compounds, e.g.1,2-benzisothiazolin-3-one or 2-n-octyl-isothiazolin-3-one, iodinecompounds, nitriles, phenols, haloalkylthio compounds or pyridinederivatives, especially 1,2-benzisothiazolin-3-one or2-n-octyl-isothiazolin-3-one. A suitable preservative is e.g. a 20% byweight solution of 1,2-benzisothiazolin-3-one in dipropylene glycol(Proxel® GXL).

The inks may also comprise further additives, such as fluorinatedpolymers or telomers, e.g. polyethoxyperfluoroalcohols (Forafac® orZonyl® products) in an amount of e.g. from 0.01 to 1% by weight, basedon the total weight of the ink.

In the inkjet printing method, individual droplets of the ink aresprayed onto a substrate in a controlled manner from a nozzle. For thispurpose, predominantly the continuous inkjet method and thedrop-on-demand method are used. In the continuous inkjet method, thedroplets are produced continuously and any droplets not required for theprinting are conveyed to a collecting vessel and recycled, whereas inthe drop-on-demand method droplets are produced and printed as required;that is to say droplets are produced only when required for theprinting. The production of the droplets can be effected, for example,by means of a piezo-inkjet head or by means of thermal energy (bubblejet). Printing by means of a piezo-inkjet head and printing inaccordance with the continuous inkjet method are preferred.

The present invention accordingly relates also to aqueous inkscomprising the dye mixtures according to the invention or the dyes offormula (2aa) according to the invention and to the use of such inks inan inkjet printing method for the printing of various substrates,especially textile fibre materials, the definitions and preferredmeanings mentioned above applying to the dye mixtures, the inks and thesubstrates.

The following Examples serve to illustrate the invention. Unlessotherwise indicated, the temperatures are given in degrees Celsius,parts are parts by weight and percentages relate to % by weight. Partsby weight relate to parts by volume in a ratio of kilograms to litres.

EXAMPLE 1 100 Parts of a Cotton Fabric are Introduced at a Temperatureof 60° C. into a Dyebath Containing 0.6 Part of the Dye of Formula

5.4 parts of the dye of formula

and 60 parts of sodium chloride in 1000 parts of water. After 45 minutesat 60° C., 20 parts of calcined soda are added. The temperature of thedyebath is maintained at 60° C. for a further 45 minutes. The dyedfabric is then rinsed and dried in customary manner. A navy blue dyeinghaving good fastness properties is obtained.

EXAMPLE 2 By Proceeding as in Example 1, But Using Instead of 0.6 Partof the Dye of Formula (101) 0.6 Part of the Dye of Formula

and using instead of 5.4 parts of the dye of formula (102) 5.4 parts ofthe dye of formula

there is likewise obtained a navy blue dyeing having good fastnessproperties.

EXAMPLES 3 TO 59 By Proceeding as in Example 1, But Using Instead of 0.6Part of the Dye of Formula (101) 0.6 Part of the Dye of the GeneralFormula

wherein D¹ _(xy) and D² _(xy) each correspond to the radicals indicatedin Table 1 and those radicals are as defined in Table 2, there arelikewise obtained navy blue dyeings having good fastness properties.TABLE 1 Ex. D¹ _(xy) D² _(xy) shade 3 D₁₁ D₁₁ navy blue 4 D₁₂ D₁₂ navyblue 5 D₁₃ D₁₃ navy blue 6 D₁₄ D₁₄ navy blue 7 D₁₅ D₁₅ navy blue 8 D₁₆D₁₆ navy blue 9 D₁₇ D₁₇ navy blue 10 D₁₈ D₁₈ navy blue 11 D₁₉ D₁₉ navyblue 12 D₂₀ D₂₀ navy blue 13 D₂₁ D₂₁ navy blue 14 D₂₂ D₂₂ navy blue 15D₂₃ D₂₃ navy blue 16 D₂₄ D₂₄ navy blue 17 D₂₅ D₂₅ navy blue 18 D₂₆ D₂₆navy blue 19 D₁₀ D₁₂ navy blue 20 D₁₂ D₁₀ navy blue 21 D₁₀ D₁₃ navy blue22 D₁₃ D₁₀ navy blue 23 D₁₀ D₂₀ navy blue 24 D₂₁ D₁₃ navy blue 25 D₁₀D₁₄ navy blue 26 D₁₀ D₁₅ navy blue 27 D₁₀ D₁₆ navy blue 28 D₁₀ D₁₇ navyblue 29 D₁₀ D₁₈ navy blue 30 D₁₀ D₁₉ navy blue 31 D₁₀ D₂₁ navy blue 32D₁₀ D₂₂ navy blue 33 D₁₀ D₂₃ navy blue 34 D₁₀ D₂₄ navy blue 35 D₁₀ D₂₅navy blue 36 D₁₀ D₂₆ navy blue 37 D₁₃ D₂₀ navy blue 38 D₁₄ D₁₁ navy blue39 D₂₉ D₃₂ navy blue 40 D₂₉ D₃₀ navy blue 41 D₂₉ D₁₀ navy blue 42 D₂₉D₃₁ navy blue 43 D₃₃ D₃₃ navy blue 44 D₂₈ D₂₈ navy blue 45 D₂₈ D₂₇ navyblue 46 D₁₀ D₂₉ navy blue 47 D₁₀ D₃₁ navy blue 48 D₁₁ D₃₁ navy blue 49D₃₁ D₁₁ navy blue 50 D₃₃ D₁₁ navy blue 51 D₃₄ D₃₄ navy blue 52 D₂₁ D₃₄navy blue 53 D₃₄ D₂₁ navy blue 54 D₃₄ D₁₀ navy blue 55 D₁₀ D₃₄ navy blue56 D₃₁ D₃₁ navy blue 57 D₁₀ D₃₃ navy blue 58 D₁₃ D₃₂ navy blue 59 D₁₉D₂₁ navy blue

TABLE 2 D_(xy)

EXAMPLES 60 TO 62 By Proceeding as in Example 1, But Using Instead of5.4 Parts of the Dye of Formula (102) 5.4 Parts of the Dye of Formula

there are likewise obtained navy blue dyeings having good fastnessproperties.

PREPARATION EXAMPLE

(a) 36.1 parts of 4-(β-sulfatoethylsulfonyl)aniline-2-sulfonic add aresuspended in 300 parts of water, dissolved to neutral with saturatedsodium carbonate solution and cooled to 0° C.; 7 parts of sodiumnitrite, 50 parts of ice and 30 parts of concentrated hydrochloric addare added and the mixture is diazotised for 2 hours. Excess nitrite isthen destroyed using sulfamic add.

(b) To the diazo solution according to (a) there is added a solution of31.9 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic add (H acid)in 500 parts of water, which solution has been adjusted to a pH of 4with hydrochloric acid. During the coupling reaction the pH ismaintained at from 3 to 3.5 with sodium acetate. There is obtained themonoazo dye that corresponds to the formula

(c) A neutral solution of 28.1 parts of4-(β-sulfatoethylsulfonyl)aniline in 100 parts of water is added to asuspension obtained by stirring a solution of 19.5 parts of cyanuricchloride in 80 parts of acetone into a mixture of 200 parts of water and200 parts of ice. The condensation reaction is continued for 1 hour withstirring at from 0 to 5° C. and at a pH of from 3 to 4. The pH ismaintained at that value by the addition of sodium hydrogen carbonate.

(d) A neutral solution of 17.6 parts of 1,3-phenylenediamine-4-sulfonicacid in 180 parts of water is added to the suspension obtained accordingto (c), and the mixture is stirred for one day at 25° C. and at a pH offrom 6.5 to 7.2. There is obtained a compound that corresponds to theformula

(e) 250 parts of ice and 60 parts of conc. hydrochloric acid are thenadded to the solution according to (d), and the mixture is cooled to 0°C. and diazotised slowly at that temperature with 7 parts of sodiumnitrite.

(f) The diazo solution according to (e) is adjusted to a pH of from 5.5to 6 with sodium hydrogen carbonate and coupled with the monoazo dyeobtained according to (b) at a pH of from 5.8 to 62. Once the reactionis complete, the reaction product is precipitated by the addition ofpotassium chloride, filtered off, washed with saturated potassiumchloride solution and dried in vacuo at 40° C. There is obtained acompound that corresponds to the formula

in the form of the free acid, and dyes cotton a navy blue shade withgood all-round fastness properties.Dyeing Procedure I

100 parts of cotton fabric are placed at 60° C. in 1500 parts of adyebath containing 45 g/n of sodium chloride and 2 parts of the reactivedye obtained according to the Preparation Example. After 45 minutes at60° C., 20 g/l of calcined soda are added. Dyeing is continued at thattemperature for a further 45 minutes. The dyed goods are then rinsed,soaped at the boil for a quarter of an hour with a non-ionic detergentrinsed again and dried.

As an alternative to the described procedure, dyeing can be carried outat 80° C. instead of at 60° C.

Dyeing Procedure II

0.1 part of the dye according to the Preparation Example is dissolved in200 parts of water, and 0.5 part of sodium sulfate, 0.1 part of alevelling agent (based on the condensation product of a higher aliphaticamine and ethylene oxide) and 0.5 part of sodium acetate are added. ThepH is then adjusted to a value of 5.5 using acetic acid (80%). Thedyebath is heated at 50° C. for 10 minutes and then 10 parts of awoollen fabric are added. The dyebath is heated to a temperature of 100°C. in the course of about 50 minutes and dyeing is carried out at thattemperature for 60 minutes. The dyebath is then cooled to 90° C. and thedyed goods are removed. The woollen fabric is washed with hot and coldwater, then spun and dried.

Printing Procedure I

While stirring rapidly, 3 parts of the dye according to the PreparationExample are sprinkled into 100 parts of a stock thickener containing 50parts of 5% sodium alginate thickener, 27.8 parts of water, 20 parts ofurea, 1 part of sodium m-nitrobenzenesulfonate and 12 parts of sodiumhydrogen carbonate. The print paste so obtained is used to print acotton fabric, drying is carried out and the resulting printed fabric issteamed in saturated steam at 102° C. for 2 minutes. The printed fabricis then rinsed, if desired soaped at the boil and again rinsed, and thendried.

Printing Procedure II

(a) Mercerised cotton satin is pad-dyed using a liquor containing 30 g/lof sodium carbonate and 50 g/l of urea (liquor uptake 70%) and dried.

(b) The cotton satin pretreated according to Step (a) is printed usingan aqueous ink containing

-   -   15% by weight of the reactive dye of formula (102) according to        the Preparation Example,    -   15% by weight of 1,2-propylene glycol, and    -   70% by weight of water        using a drop-on-demand inkjet head (bubble jet). The print is        dried completely and fixed in saturated steam at 102° C. for 8        minutes, cold-rinsed, washed off at the boil, rinsed again and        dried.

1. A dye mixture comprising at least one dye of formula

together with at least one dye of formula

wherein R₁ and R₂ are each independently of the other hydrogen orunsubstituted or substituted C₁-C₈alkyl, (R₃)₀₋₃ and (R₄)₀₋₃ eachindependently of the other denote from 0 to 3 identical or differentsubstituents from the group halogen, C₁-C₄alkyl, C₁-C₄alkoxy, carboxyand sulfo, D₁ and D₂ are each independently of the other the radical ofa diazo component of the benzene or naphthalene series, r and s are eachindependently of the other the number 0 or 1, and the sum of r+s is thenumber 1 or 2, Y₁ and Y₂ are each independently of the other afibre-reactive radical of formula—SO₂-Z  (3a),—NH—CO—(CH₂)_(m)—SO₂-Z  (3b),—CONH—(CH₂)_(n)—SO₂-Z  (3c),—NH—CO—CH(Hal)-CH₂-Hal  (3d),—NH—CO—C(Hal)═CH₂  (3e) or

wherein X is halogen, T has independently the same definitions as X, oris a non-fibre-reactive substituent or a fibre-reactive radical offormula

(R₅)₀₋₂ denotes from 0 to 2 identical or different substituents from thegroup halogen, C₁-C₄-alkyl, C₁-C₄alkoxy and sulfo, Z is vinyl or aradical —CH₂—CH₂—U and U is a group removable under alkaline conditions,Q is a group —CH(Hal)-CH₂-Hal or —C(Hal)═CH₂, m and n are eachindependently of the other the number 2, 3 or 4, and Hal is halogen,with at least one of the radicals Y₁ and Y₂ being a radical of formula(3f), and the dye of formula (2) not being a dye of formula

wherein X* is fluorine and the β-sulfatoethylsulfonyl group is bonded inthe 4-position, or X* is chlorine and the β-sulfatoethylsulfonyl groupis bonded in the 3-position.
 2. A dye mixture according to claim 1,wherein D₁ and D₂ are each independently of the other a radical offormula

wherein (R₆)₀₋₃ denotes from 0 to 3 identical or different substituentsfrom the group halogen, C₁-C₄-alkyl, C₁-C₄alkoxy, carboxy, nitro andsulfo, and Y₃ is a radical of formula (3a), (3b), (3c), (3d), (3e) or(3f) according to claim
 1. 3. A dye mixture according to claim 1,wherein D₁ and D₂ are each independently of the other a radical offormula

wherein (R_(6a))₀₋₂ denotes from 0 to 2 identical or differentsubstituents from the group halogen, C₁-C₄-alkyl, C₁-C₄alkoxy and sulfo,Y_(3a) is α,β-dibromopropionylamino or α-bromoacryloylamino, m is thenumber 2 or 3, n is the number 2 or 3, and Z₁, Z₂, Z₃ and Z₄ are eachindependently of the others vinyl, β-chloroethyl or β-sulfatoethyl.
 4. Adye mixture according to claim 1, wherein R₁ and R₂ are hydrogen.
 5. Adye mixture according to claim 1, wherein R₁ and R₂ are hydrogen, D₁ isa radical of formula

D₂ is a radical of formula

wherein R_(6a) and R_(6b) are each independently of the other methyl ormethoxy, and Z_(1a) and Z_(1b) are each independently of the othervinyl, β-chloroethyl or β-sulfatoethyl.
 6. A dye mixture according toclaim 1, wherein the dye of formula (2) is a dye of formula

wherein (R₃)₀₋₂ and (R₄)₀₋₂ each independently of the other denote from0 to 2 identical or different substituent selected from the groupC₁-C₄alkyl, C₁-C₄alkoxy and sulfo, and one of the fibre-reactiveradicals Y₁ and Y₂ is a radical of formula (3a), (3b), (3c), (3d) or(3e), and the other of the fibre-reactive radicals Y₁ and Y₂ is aradical of formula (3f), the meanings according to claim 1 applying forthe fibre-reactive radicals of formulae (3a), (3b), (3c), (3d), (3e) and(3f).
 7. A method of dyeing or printing of hydroxyl-group-containing ornitrogen-containing fibre materials, which comprises contacting saidmaterials with a dye mixture according to claim
 1. 8. A dye of formula

wherein X is halogen, and Z₅ and Z₄ are each independently of the othervinyl or a radical —CH₂—CH₂—U and U is a group removable under alkalineconditions.
 9. A method of dying or printing ofhydroxyl-group-containing or nitrogen-containing fibre materials, whichcomprises contacting said materials with a dye of formula (2aa)according to claim
 8. 10. An aqueous ink comprising a dye mixtureaccording to claim
 1. 11. An inkjet printing method for printinghydroxyl-group-containing or nitrogen-containing fibre materials, whichcomprises printing said materials with an aqueous ink according to claim10.
 12. An aqueous ink comprising a dye according to claim 8.